JP4622369B2 - Process for producing molded product of polyphenylene oxide resin composition - Google Patents

Description

  The present invention relates to a method for producing a polyphenylene oxide-based resin composition molded body.

  Polyphenylene oxide, a type of engineering plastic, has excellent heat resistance and electrical insulation, and has a low dielectric constant compared to other engineering plastics such as polyethersulfone, polyetheretherketone, polyetherimide, and polyamideimide. It has a characteristic that it is a rate and is relatively inexpensive.

  And as a molded object using polyphenylene oxide, for example, films using a resin composition comprising polyphenylene oxide and a copolymer having a functional group reactive with polyphenylene oxide are known. (Patent Document 1).

However, the molded body using the polyphenylene oxide-based resin composition has a problem that chemical resistance to a solvent, particularly a halogenated hydrocarbon solvent typified by carbon tetrachloride, is not sufficient. The development of molded articles such as films made of the resin composition is hindered.
An object of the present invention is a production method that can be obtained from a resin composition comprising a polyphenylene oxide and a copolymer having a functional group reactive with the polyphenylene oxide, and can obtain a molded article having excellent chemical resistance. Is to provide.

JP 2002-319316 A

  As a result of intensive studies to solve the above problems, the inventors of the present invention molded a resin composition comprising polyphenylene oxide and a copolymer having a functional group reactive with polyphenylene oxide, and a specific temperature. It was found that a polyphenylene oxide-based resin composition molded article excellent in chemical resistance can be obtained by heat treatment in the range, and the present invention was completed.

（式中、Ｒ₁およびＲ₂は、それぞれ独立に水素原子又は置換基を有していてもよい全炭素数１〜２０の炭化水素基を表す。）
で示される構造単位を有するポリフェニレンオキサイド（Ａ）と該ポリフェニレンオキサイドと反応性を有する官能基を持った共重合体（Ｂ）とからなる樹脂組成物を成形して製造した成形体を、（Ｔｇ−４０）［℃］以上（Ｔｇ＋５０）［℃］以下（Ｔｇ：上記樹脂組成物のガラス転移温度［℃］）の範囲で熱処理することを特徴とするポリフェニレンオキサイド系樹脂組成物成形体の製造方法を提供するものである。 That is, the present invention
The following formula (1)

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.)
A molded product produced by molding a resin composition comprising a polyphenylene oxide (A) having a structural unit represented by formula (B) and a copolymer having a functional group reactive with the polyphenylene oxide (Tg), -40) A method for producing a polyphenylene oxide-based resin composition molded article, wherein the heat treatment is performed within a range of [° C.] to (Tg + 50) [° C.] (Tg: glass transition temperature [° C.] of the resin composition). Is to provide.

  According to the production method of the present invention, a polyphenylene oxide-based resin composition molded article having excellent chemical resistance can be obtained.

  In the method for producing a molded article of a polyphenylene oxide resin composition of the present invention, first, a polyphenylene oxide (A) having a structural unit represented by the above formula (1) and a copolymer having a functional group reactive with the polyphenylene oxide are used. A resin composition comprising the polymer (B) is molded.

（式中、Ｒ₁およびＲ₂は前記と同じ意味を有する。）
で示されるフェノール化合物の少なくとも１種から誘導し得る。 First, the resin composition used for manufacture of the polyphenylene oxide resin composition molded article of the present invention will be described.
The polyphenylene oxide which is the component (A) of the resin composition has the structural unit of the formula (1). For example, the following formula (2)

(In the formula, R ₁ and R ₂ have the same meaning as described above.)
It can derive from at least 1 sort (s) of a phenolic compound shown by these.

Here, R ₁ and R ₂ each independently represent hydrogen or a hydrocarbon having 1 to 20 carbon atoms which may have a substituent, but may have 1 substituent. -20 hydrocarbons include, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, pentyl, cyclopentyl, hexyl and cyclohexyl. Group, octyl group, decyl group and other alkyl groups having 1 to 20 carbon atoms, phenyl group, 4-methylphenyl group, 1-naphthyl group, 2-naphthyl group and other aryl groups having 6 to 20 carbon atoms, benzyl group, 2-phenylethyl A substituent such as an aralkyl group having 7 to 20 carbon atoms such as a 1-phenylethyl group, a trifluoromethyl group, a 2-t-butyloxyethyl group, and a 3-diphenylaminopropyl group. Such total hydrocarbon group having 1 to 20 carbon atoms that can be mentioned.

Among these, R ₁ and R ₂ are preferably hydrogen, a methyl group or the like, and particularly preferably hydrogen.

  Even if the polyphenylene oxide as component (A) is a polymer of the phenol compound represented by the formula (2), the phenol compound represented by the formula (2) and other phenol compounds such as bisphenol-A, tetra A copolymer with a polyvalent hydroxyaromatic compound such as bromobisphenol-A, resorcin, hydroquinone, or novolak resin may be used. Such a copolymer preferably contains 80 mol% or more, more preferably 90 mol% or more of the structural unit of the formula (1) derived from the formula (2).

  The polyphenylene oxide as the component (A) can be produced by subjecting the above phenol compound to oxidative polymerization with oxygen or an oxygen-containing gas using an oxidative coupling catalyst. The oxidative coupling catalyst is not particularly limited, and any catalyst having a polymerization ability can be used. For example, typical examples thereof include a catalyst containing cuprous chloride and a catalyst containing divalent manganese salts.

In addition, the intrinsic viscosity [η] of the component (A) in the present invention is preferably in the range of 0.30 to 0.65, more preferably 0.35 to 0.50 (25 ° C., chloroform solution).
When [η] is less than 0.30, the heat resistance of the composition tends to decrease, and when [η] exceeds 0.65, the molding processability of the composition tends to decrease.

  The resin composition used in the present invention contains a resin composition comprising a polyphenylene oxide of component (A) as described above and a copolymer having a functional group reactive with the polyphenylene oxide of component (B). However, the functional group having reactivity with the polyphenylene oxide is only required to have reactivity with the component (A), and examples thereof include an oxazolyl group, an epoxy group, and an amino group. An epoxy group is preferable.

  In the copolymer which is the component (B), the method for introducing such a functional group into the copolymer is not particularly limited, and can be performed by a known method. For example, at the copolymer synthesis stage, it is possible to introduce a monomer having the functional group by copolymerization, or to graft copolymerize the monomer having the functional group to the copolymer. It is.

（式中、Ｒは、エチレン系不飽和結合を有する炭素数２〜１３の炭化水素基を表し、Ｘは、−Ｃ(Ｏ)Ｏ−、−ＣＨ₂−Ｏ−または

を表す。）
で示される不飽和カルボン酸グリシジルエステル、不飽和グリシジルエーテルが好ましく用いられる。 Among the monomers having such a functional group, a monomer containing a glycidyl group is particularly preferably used as the functional group that is an epoxy group. As a monomer containing a glycidyl group, for example, the following general formula

(In the formula, R represents a hydrocarbon group having 2 to 13 carbon atoms having an ethylenically unsaturated bond, and X represents —C (O) O—, —CH ₂ —O— or

Represents. )
An unsaturated carboxylic acid glycidyl ester or an unsaturated glycidyl ether represented by formula (1) is preferably used.

  Examples of the unsaturated carboxylic acid glycidyl ester include glycidyl acrylate, glycidyl methacrylate, itaconic acid diglycidyl ester, butenetricarboxylic acid triglycidyl ester, and p-styrene carboxylic acid glycidyl ester.

Examples of the unsaturated glycidyl ether include vinyl glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, methacryl glycidyl ether, and styrene-p-glycidyl ether.
Specifically, unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether are preferably used.

  The copolymer (B) having a functional group reactive with the polyphenylene oxide contains 0.1 to 30% by mass of the unsaturated carboxylic acid glycidyl ester unit and / or the unsaturated glycidyl ether unit. Is preferable, and it is more preferable to contain 0.1-20 mass%.

  The copolymer (B) having a functional group reactive with polyphenylene oxide may be a rubber, a thermoplastic resin, or a mixture of rubber and a thermoplastic resin.

  Examples of the rubber as the component (B) of the present invention include acrylic rubber having a functional group reactive with polyphenylene oxide, and vinyl aromatic hydrocarbon compound-conjugated diene compound block having a functional group reactive with polyphenylene oxide. Copolymer rubber can also be illustrated.

The acrylic rubber having a functional group reactive with polyphenylene oxide is preferably represented by the general formulas (8) to (10).
^{_{CH 2 = CR 7 -C (O}} ) -OR 1 (8)
^{_{CH 2 = CR 8 -C (O}} ) -OR 2 OR 3 (9)
^{_{CH 2 = CR 4 H-C}} (O) -O (R 5 (C (O) O) nR 6 (10)
(In the formula, R ¹ represents an alkyl group having 1 to 18 carbon atoms (preferably 1 to 8) or a cyanoalkyl group having 1 to 18 carbon atoms. R ² represents an alkylene group having 1 to 12 carbon atoms. , R ³ represents an alkyl group having 1 to 12 carbon atoms, R ⁴ , R ⁷ and R ⁸ each independently represents a hydrogen atom or a methyl group, R ⁵ represents an alkylene group having 3 to 30 carbon atoms, R ⁶ Represents an alkyl group having 1 to 20 carbon atoms or a derivative thereof, and n represents an integer of 1 to 20).
And at least one monomer selected from the compounds represented by formula (1) and a monomer having a functional group reactive with polyphenylene oxide.

Specific examples of the (meth) acrylic acid alkyl ester represented by the general formula (8) include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, butyl acrylate, pentyl acrylate, and hexyl. Acrylate, actyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, cyanoethyl acrylate, methyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, and the like. Methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, t rt- butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate are preferred.
In addition, as (meth) acrylic acid ester, the 1 type may be used independently or 2 or more types may be used together.

  Examples of the acrylic acid alkoxyalkyl ester represented by the general formula (9) include, for example, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxypropyl acrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, butoxyethyl methacrylate. Examples thereof include acrylate and ethoxypropyl methacrylate. One or more of these can be used as a component of the acrylic rubber.

As a constituent component of the acrylic rubber, an unsaturated monomer copolymerizable with at least one monomer selected from the compounds represented by the general formulas (8) to (10) is used as necessary. Can do.
Examples of such unsaturated monomers include ethylene, styrene, α-methyl styrene, acrylonitrile, halogenated styrene, methacrylonitrile, acrylamide, methacrylamide, vinyl naphthalene, N-methylol acrylamide, vinyl acetate, vinyl chloride. , Vinylidene chloride, benzyl acrylate, methacrylic acid, itaconic acid, fumaric acid, maleic acid and the like.

  As the monomer having a functional group reactive with polyphenylene oxide, unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether are preferable. In this case, the preferable component ratio is at least one monomer selected from the compounds represented by the general formulas (8) to (10) 40.0 to 99.9% by mass, unsaturated carboxylic acid glycidyl ester, and And / or at least one monomer selected from the compounds represented by the above general formulas (8) to (10), 0.1 to 30% by weight, preferably 0.1 to 20% by weight, of unsaturated glycidyl ether; The copolymerizable unsaturated monomer is 0.0 to 30% by mass. When the component ratio of the acrylic rubber is within the above range, the composition has good heat resistance, moldability and the like, which is preferable.

  The method for producing the acrylic rubber is not particularly limited, and is described, for example, in JP 59-1113010, JP 62-64809, JP 3-160008, or WO 95/04764. Such a known polymerization method can be used, and it can be produced by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization in the presence of a radical initiator.

Among the copolymers (B), rubber having an epoxy group is preferable, and (meth) acrylic acid ester-ethylene- (unsaturated carboxylic acid glycidyl ester and / or an (acrylic) rubber having an epoxy group. Unsaturated glycidyl ether) copolymer rubber and the like are more preferable.

The copolymer (B) having a Mooney viscosity of 3 to 70 is preferable, 3 to 30 is more preferable, and 4 to 25 is particularly preferable.
The Mooney viscosity here refers to a value measured using a 100 ° C. large rotor according to JIS K6300.

In order to improve the thermal stability and mechanical properties of the resulting molded article, the (meth) acrylic acid ester unit exceeds 40% by mass and is less than 96% by mass, more preferably 45 to 70% by mass, and the ethylene unit is 3% by mass. % To less than 50% by weight, more preferably 10 to 49% by weight, 0.1 to 30% by weight, more preferably 0.1 to 20% by weight of unsaturated carboxylic acid glycidyl ether unit and / or unsaturated glycidyl ether unit. It is. (Representative polymerization methods: methods described in JP-A-48-11388, JP-A-61-127709, etc., for example, in the presence of a polymerization initiator that generates free radicals, a pressure of 500 kg / cm ² or more And can be produced under conditions of a temperature of 40 to 300 ° C.)

Examples of the vinyl aromatic hydrocarbon compound in the vinyl aromatic hydrocarbon compound-conjugated diene compound block copolymer rubber having a functional group reactive with polyphenylene oxide include styrene, vinyl toluene, divinylbenzene, and α-methylstyrene. , P-methylstyrene, vinylnaphthalene, etc., among which styrene is preferable. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 3-butyl-1,3-octadiene, and butadiene or isoprene is preferable.
Such a vinyl aromatic hydrocarbon compound-conjugated diene compound block copolymer or a hydrogenated product thereof can be produced by a known method, for example, Japanese Patent Publication No. 40-23798 and Japanese Patent Publication No. 59-133203. Etc. are described.
The vinyl aromatic hydrocarbon compound-conjugated diene compound block copolymer rubber having a functional group reactive with polyphenylene oxide in the present invention is a vinyl aromatic hydrocarbon compound-conjugated diene compound block obtained by the above-described method or the like. It can be obtained by introducing a monomer having reactivity with polyphenylene oxide, such as an epoxy group, into the copolymer. The method for introducing such a monomer into the vinyl aromatic hydrocarbon compound-conjugated diene compound block copolymer is not particularly limited, but is preferably introduced by graft copolymerization or the like.

  The rubber as the copolymer (B) used in the present invention can be vulcanized as necessary and used as a vulcanized rubber.

  Vulcanization of the above (meth) acrylic acid ester-ethylene- (unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether) copolymer rubber is a polyfunctional organic acid, polyfunctional amine compound, imidazole compound, etc. However, the present invention is not limited to these.

  On the other hand, as a thermoplastic resin having an epoxy group as a specific example of the copolymer (B) having a functional group reactive with polyphenylene oxide, (a) an ethylene unit is 60 to 99% by mass; An epoxy group-containing ethylene copolymer comprising 0.1 to 20% by mass of a saturated carboxylic acid glycidyl ester unit and / or an unsaturated glycidyl ether unit and (c) 0 to 40% by mass of an ethylenically unsaturated ester compound unit is exemplified. be able to.

  Examples of the ethylenically unsaturated ester compound (c) include vinyl acetate, vinyl propionate, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and other carboxylic acid vinyl esters. , Α, β-unsaturated carboxylic acid alkyl esters and the like. In particular, vinyl acetate, methyl acrylate, and ethyl acrylate are preferable.

  Examples of the epoxy group-containing ethylene copolymer include a copolymer composed of ethylene units and glycidyl methacrylate units, a copolymer composed of ethylene units, glycidyl methacrylate units and methyl acrylate units, ethylene units, glycidyl methacrylate units and acrylic acid. Examples thereof include a copolymer composed of ethyl units, a copolymer composed of ethylene units, glycidyl methacrylate units and vinyl acetate units.

  The melt index (hereinafter sometimes referred to as MFR. JIS K6760, 190 ° C., 2.16 kg load) of the epoxy group-containing ethylene copolymer is preferably 0.5 to 100 g / 10 minutes, more preferably 2 to 50 g. / 10 minutes. The melt index may be outside this range, but if the melt index exceeds 100 g / 10 min, it is not preferable in terms of mechanical properties when it is made into a composition, and if it is less than 0.5 g / 10 min, component (A) The compatibility with is inferior.

The epoxy group-containing ethylene copolymer is preferably in the range stiffness modulus of 10~1300kg / cm ^2, further preferably from 20~1100kg / cm ^2. If the bending rigidity is outside this range, the moldability and mechanical properties of the composition may be insufficient.

  The copolymer (B) is preferably a copolymer having a heat of fusion of crystals of less than 3 J / g in order to improve the thermal stability and flexibility of the molded article of the present invention.

  The epoxy group-containing ethylene copolymer is usually an unsaturated epoxy compound and ethylene in the presence of a radical generator at 500 to 4000 atm and 100 to 300 ° C. in the presence or absence of a suitable solvent or chain transfer agent. It is produced by a high pressure radical polymerization method for copolymerization. It can also be produced by a method in which an unsaturated epoxy compound and a radical generator are mixed with polyethylene and melt graft copolymerized in an extruder.

  The ratio of the component (A) polyphenylene oxide of the resin composition in the present invention to the component (B) copolymer having a functional group having reactivity with the polyphenylene oxide is usually 99 to 1 for the component (A). The mass%, preferably 99 to 40 mass%, and component (B) is usually 1 to 99 mass%, preferably 1 to 60 mass%. If the amount of the component (A) is too small, the heat resistance of the composition tends to be remarkably lowered. If the amount of the component (A) is too large, the moldability of the composition tends to be insufficient.

  In the resin composition used in the present invention, although the details of the mechanism are unknown, a reaction is induced between the component (A) and the component (B) of the composition, and therefore the moldability of the resin composition is increased. Is thought to improve.

  The resin composition used in the present invention includes an organic filler, an antioxidant, a heat stabilizer, a light stabilizer, a flame retardant, a lubricant, an inorganic or organic colorant, a rust inhibitor, a crosslinking agent, and a foam as necessary. Various additives such as an agent, a fluorescent agent, a surface smoothing agent, a surface gloss improving agent, and a mold release improving agent such as a fluororesin may be contained.

  The above resin composition is molded into a desired shape by various molding methods such as extrusion molding, injection molding, rotational molding, compression molding, blow molding, blow molding, transfer molding, press molding, and solution casting. In this manner, a molded body (primary molded body) to be subjected to heat treatment can be obtained. The primary molded body in the present invention is excellent in heat resistance, impact resistance, electrical properties, flame retardancy, and the like. . Moreover, the polyphenylene oxide-type resin composition molded object with favorable chemical resistance can be obtained by using said primary molded object for heat processing.

As the shape of the primary molded body, films (films, sheets, etc.), plates, filaments, non-woven fabrics, woven fabrics, tubes, tubes, pipes, containers, bottles, deformed products, home appliance parts, electric / electronic parts, mobile Examples include equipment parts, electric parts, automobile parts (bumpers, instruments, etc.), automobile outer plate members, housing materials, and the like.
Usually, the shape of the polyphenylene oxide resin composition molded body produced by the method of the present invention is substantially the same as the shape of the primary molded body.

  In order to obtain the films by molding the above resin composition, for example, an extrusion molding method can be adopted, and specifically, a method of supplying the above resin composition to an extruder equipped with a die (die). Can be used.

  As a die used for manufacturing films, a T die and a cylindrical slit die are preferably used. A casting method, a hot press method, and the like can also be applied to the production of films based on Patent Document 1.

  Further, in order to obtain a hollow molded body such as a container by molding the resin composition, for example, a blow molding method can be adopted, specifically, using a blow molding machine, A method can be used in which fluid pressure such as air or water is blown into the mold so as to be in close contact therewith.

  Moreover, in order to obtain the tube and tube by molding the resin composition, for example, an extrusion molding method can be employed. Specifically, the resin composition is removed from the extruder using a tube molding machine. A method of melt extrusion to a tube die can be used.

  Further, in order to obtain the filament by molding the above resin composition, a method in which the resin composition is melt-extruded to a strand die by an extruder and then wound at a high speed can be used.

  In addition, in order to obtain a molded body by injection molding of the resin composition, a method of injecting the molten resin composition from an extruder into a mold at a high pressure can be used using an injection molding machine. .

  In the method for producing a polyphenylene oxide-based resin composition molded body of the present invention, it is necessary to heat-treat the primary molded body in the range of (Tg-40) [° C.] to (Tg + 50) [° C.]. Here, Tg [° C.] means the glass transition temperature of the resin composition.

The temperature of the heat treatment is (Tg−40) [° C.] or more and (Tg + 50) [° C.] or less, and more preferably (Tg−30) [° C.] or more and (Tg + 30) [° C.] or less. When the heat treatment temperature exceeds (Tg + 50) [° C.], the primary molded body is significantly deformed by heat, and when the heat treatment temperature is less than (Tg−40) [° C.], the effect of the present invention is small. The Tg of the resin composition used in the invention can usually be determined by thermomechanical analysis (hereinafter abbreviated as TMA).

  The atmosphere for the heat treatment may be air or an inert gas such as nitrogen or argon.

The heat treatment can be performed, for example, in a drying furnace or a dryer equipped with a heater. Especially, it is preferable to heat-process in a hot air circulation type dryer.
Further, the heat treatment may be performed batchwise or continuously.

Although the heat treatment time is not particularly specified, it can be appropriately determined according to the use of the molded body and the heat treatment temperature, but it is usually about 1 to 48 hours, and preferably 1 to 24 hours.
When the primary molded body is a film such as a film or a sheet, the film can be heat-treated by fixing the film with an instrument in order to suppress deformation of the film due to heat treatment.

（式中、Ｒ₁およびＲ₂は、それぞれ独立に水素原子又は置換基を有していてもよい全炭素数１〜２０の炭化水素基を表す。）
で示される構造単位を有するポリフェニレンオキサイド（Ａ）と該ポリフェニレンオキサイドと反応性を有する官能基を持った共重合体（Ｂ）とからなる樹脂組成物を成形して製造した成形体を、（Ｔｇ−４０）［℃］以上（Ｔｇ＋５０）［℃］以下（Ｔｇ：上記樹脂組成物のガラス転移温度［℃］）の範囲で熱処理することにより製造されたポリフェニレンオキサイド系樹脂組成物成形体である。 The first polyphenylene oxide-based resin composition molded article of the present invention has the following formula (1):

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.)
A molded product produced by molding a resin composition comprising a polyphenylene oxide (A) having a structural unit represented by formula (B) and a copolymer having a functional group reactive with the polyphenylene oxide (Tg), -40) A polyphenylene oxide-based resin composition molded article produced by heat treatment in the range of [° C.] to (Tg + 50) [° C.] (Tg: glass transition temperature [° C.] of the resin composition).

The second polyphenylene oxide resin composition molded body of the present invention is
A molded body using the above polyphenylene oxide (A) and the above copolymer (B), wherein the weight reduction rate X measured under the following conditions is 70% or less.
X = (Ma-Mb) / Ma × 100
(Ma: Weight of the test piece cut out from the molded body Mb: Weight of the test piece after the test piece was immersed in carbon tetrachloride at 25 ± 2 ° C. for 120 hours and dried)

The second polyphenylene oxide-based resin composition molded article of the present invention can be produced by the production method of the present invention. Among these, X is preferably 60% or less, more preferably 40% or less, and particularly preferably substantially 0%.

Examples of the polyphenylene oxide resin composition molded body of the present invention and the (primary) molded body of the present invention include a molded body (injection molded body) manufactured by an injection molding method.
Examples of the injection molded body include automobile parts, electric / electronic parts, electric transmission parts, mobile device parts, housing materials, and the like.

Another embodiment includes a molded body (blow molded body) produced by a blow molding method.
Examples of the injection-molded body include an automobile outer plate member, a bottle or a container.

Moreover, the molded object (extruded molded object) manufactured by the extrusion method is mention | raise | lifted.
Examples of the extruded product include films, tubes, and pipes.

  When the molded body is a film, the thickness is not particularly limited, but a range of 1 to 1000 μm is practically preferable, and a range of 1 to 500 μm is more preferable. The surface of the film can be subjected to a surface treatment as necessary. Examples of such surface treatment methods include corona discharge treatment, plasma treatment, flame treatment, infrared treatment, sputtering treatment, solvent treatment, and polishing treatment. These treatments may be performed during the molding process or may be performed on the film or sheet after the molding process. However, such a process may be performed in the molding process, particularly before the winder. preferable.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited only to these.

(1) Physical property measurement
(i) Thermal properties (glass transition temperature, Tg)
As a measurement sample, a film formed as a primary molded body and a dumbbell-shaped injection molded body cut into a strip shape having a width of 5 mm and a length of 20 mm were used. (In the case of films, the film MD cut out in the length direction is used. In the case of a dumbbell-shaped injection-molded product, the center portion of the dumbbell is used.) Measurement was performed by TMA according to JIS K7197.
Specifically, the glass transition point is described in Seiko Instrument, Inc. , Manufactured by EXSTAR TMA / SS6100, was measured in a nitrogen atmosphere at a heating rate of 5 ° C./min, a load of 5 kgf, and a measurement temperature range of 23 to 250 ° C.

(ii) Chemical resistance test The chemical resistance test was conducted as follows. A 50 cc carbon tetrachloride is put into a glass container, and a film of a polyphenylene oxide composition cut into a 2 cm square is immersed therein. Next, after covering and sealing the glass container, it is immersed for 120 hours at room temperature. Thereafter, the film is taken out from the liquid and vacuum dried. The chemical resistance is evaluated from the change in weight of the film before and after immersion.
X = (Ma-Mb) / Ma × 100
(Ma: Weight of the test piece cut out from the molded body Mb: (Ma: Weight of the test piece cut out from the molded body Mb: The test piece was immersed in carbon tetrachloride at 25 ± 2 ° C. for 120 hours, taken out and dried.) After test piece weight)

(Iii) Deflection temperature under load (heat resistance)
The resin test piece was cut into strips, and the temperature at which the test piece reached a certain deflection (load deflection temperature) was measured with a load of 18.5 kg according to JIS K-7191.

(iv) Tensile strength and elongation rate Using an Autograph A-10TD model manufactured by Shimadzu Corporation, a tensile test was performed at room temperature and a tensile speed of 5 mm / min in accordance with JIS K-7161, and the sample was broken. The tensile strength and elongation at that time were measured. Asked.

(v) Izod impact strength After notching the resin specimen, an Izod impact test was performed at room temperature in accordance with JIS K-7110.

(2) Resin composition component (A)
As component (A), Mitsubishi Gas Chemical Co., Ltd., polyphenylene oxide, YPX-100D ([η] = 0.4) was used.
Ingredient (B)
(B-1, 2 added)

The following were used as the component (B).
B-1: manufactured by Sumitomo Chemical Co., Ltd., Bond First E (ethylene / glycidyl methacrylate = 88/12 weight ratio, MFR (190 ° C.) = 3 g / 10 min)
B-2: manufactured by Sumitomo Chemical Co., Ltd., Bond First 7L (ethylene / glycidyl methacrylate / methyl acrylate = 67/3/30 weight ratio, MFR (190 ° C.) = 10 g / 10 min)

Reference example 1
After the component (A) and the component (B-1) are dried at 80 ° C. for 15 hours, the components (A) / component (B-1) = 80/20 (weight ratio) are mixed well. , Using twin screw extruder, Berstolf ZE40A (screw diameter 43mm, L / D = 40), cylinder setting temperature 290 ° C, rotation speed 150rpm, resin feed rate about 10Kg / hr, melt-kneading while venting Was done.
The pellets of the obtained composition were used in a polylab system manufactured by Hake Co., Ltd. (single screw extruder 19.05 mm, L / D = 20, cylinder set temperature 280 ° C., screw rotation) Kneading and extrusion were performed at several 33 rpm. A T die having a slit gap of 0.8 mm and a die width of 100 mm was used, and film formation was performed at a resin temperature of 280 ° C. in the T die. Here, the resin temperature in the T die was detected by a temperature detector on the lower wall surface of the die portion wall approximately 2 cm inside from the T die exit. The resin coming out of the T die was wound at 3.8 m / min using a three-roll winder to obtain a film having a thickness of 280 μm. Hereinafter, the film may be abbreviated as A-1.
The Tg of A-1 was 198 ° C.

Comparative Example 1
When the chemical resistance test of the above A-1 film was conducted, the film was dissolved in carbon tetrachloride after 120 hours of immersion in carbon tetrachloride, and partly finely dispersed and cannot be taken out. Met.

Example 1
Place the A-1 film in a dryer and place the A-1 film at 185 ° C in an air atmosphere.
After heat treatment and heating at (Tg-13 ° C.) for 20 hours, it was taken out and subjected to a chemical resistance test. After the chemical resistance test, the film taken out from the liquid was vacuum-dried at 120 ° C. for 1 hour to determine the change in weight. The weight loss (X) of the heat treated film was almost zero.

Example 2
The weight change before and after the chemical resistance test was determined in the same manner as in Example 1 except that the heat treatment of the A-1 film was 185 ° C. (Tg-13 ° C.) for 4 hours. The weight loss (X) here was 51%.

Example 3
The weight change before and after the chemical resistance test was determined in the same manner as in Example 1 except that the heat treatment of the A-1 film was 195 ° C. (Tg−3 ° C.) for 4 hours. The weight loss (X) here was 20%.

Comparative Example 2
The chemical resistance test was conducted in the same manner as in Example 1 except that the heat treatment of the A-1 film was 150 ° C. (Tg-48 ° C.) for 1 hour. After the test, the film was carbon tetrachloride. Dissolved in, partially dispersed finely, it was impossible to take out.

Reference example 2
The component (A) is dried at 120 ° C. for 8 hours, the component (B-2) is dried at 60 ° C. for 4 hours, and then the component (A) / component (B-2) = 95/5 (weight) After mixing well at a ratio of 2), a twin-screw extruder manufactured by Technobel Co., Ltd., TZW-15-30MG (screw diameter 15mm, L / D = 30) was used, and the cylinder set temperature, cylinder set temperature 290 ° C, Melt kneading was performed while degassing with a vent at a screw rotation speed of 150 rpm. The composition thus obtained is hereinafter sometimes abbreviated as a-2.

Comparative Example 3 and Example 4
Using the Niigata Iron Works Co., Ltd. injection molding machine NIIGATA NN75, the a-2 pellets were set at a cylinder setting temperature of 295 ° C., a mold temperature of 90 ° C., an injection pressure of 1650 Kg / cm ² , and an extruder screw speed of 50 rpm. Injection molding was performed. As the mold, a dumbbell-shaped mold having a length of 175 mm, a thickness of 3.2 mm, and a width of a constricted portion of 12.5 mm was used. By such injection molding, it was possible to obtain a test piece having a uniform light brown color and a smooth surface. Table 1 shows the physical properties of the obtained test specimen, a-3. The Tg of a-3 was 209 ° C.

Next, the test piece obtained by the above injection molding was heat-treated at 200 ° C. (Tg−9 ° C.) for 2 hours. Table 1 shows the physical properties of the specimen a-4 after the heat treatment.

Claims (21)

The following formula (1)

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.)
A molded body produced by molding a resin composition comprising a polyphenylene oxide (A) having a structural unit represented by formula (B) and a copolymer having a functional group reactive with the polyphenylene oxide (Tg) -40) A method for producing a polyphenylene oxide-based resin composition molded article, wherein the heat treatment is performed in a range of [° C.] or more and (Tg + 50) [° C.] or less (Tg: glass transition temperature [° C.] of the resin composition). .   The method for producing a molded body according to claim 1, wherein the heat treatment time is 1 to 48 hours.   The production method according to claim 1 or 2, wherein the copolymer (B) having a functional group reactive with polyphenylene oxide is a copolymer having an epoxy group.   The copolymer having an epoxy group is a copolymer containing 0.1 to 30% by mass of an unsaturated carboxylic acid glycidyl ester unit and / or an unsaturated glycidyl ether unit. Production method.   The production method according to any one of claims 1 to 4, wherein the heat of fusion of the copolymer (B) is less than 3 J / g.   The production method according to any one of claims 1 to 5, wherein the copolymer (B) has a Mooney viscosity in the range of 3 to 70.   The production method according to claim 3, wherein the copolymer having an epoxy group is a rubber having an epoxy group.   8. The production method according to claim 7, wherein the rubber having an epoxy group comprises a (meth) acrylic acid ester-ethylene- (unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether) copolymer rubber. .   (Meth) acrylic acid ester is at least one selected from methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate The manufacturing method of Claim 8 containing.   The copolymer having an epoxy group comprises (a) 60 to 99% by mass of ethylene units, (b) 0.1 to 20% by mass of unsaturated carboxylic acid glycidyl ester units and / or unsaturated glycidyl ether units, (c The method for producing a molded article according to any one of claims 3 to 5, which is an epoxy group-containing ethylene copolymer comprising 0 to 40% by mass of an ethylenically unsaturated ester compound unit.   The method according to claim 1, wherein the molded body is a film.   The manufacturing method according to claim 1, wherein the molded body is an injection molded body.   A polyphenylene oxide-based resin composition molded article produced by the method according to claim 1. The following formula (1)

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.)
A molded product comprising a resin composition comprising a polyphenylene oxide (A) having a structural unit represented by formula (B) and a copolymer (B) having a functional group reactive with the polyphenylene oxide, The polyphenylene oxide-based resin composition molded article, wherein the weight reduction rate X represented by (3) is 70% or less.
X = (Ma−Mb) / Ma × 100 (3)
(Ma: Weight of the test piece cut out from the molded body Mb: Weight of the test piece after the test piece was immersed in carbon tetrachloride at 25 ± 2 ° C. for 120 hours and dried)
The molded body according to claim 13 or 14 , wherein the molded body is a molded body manufactured by an injection molding method. The molded body according to claim 15 , wherein the molded body has a shape of an automobile part, an electric / electronic part, a power transmission part, a mobile device part or a housing material. The molded body according to claim 13 or 14 , wherein the molded body is a molded body manufactured by a blow molding method. The shaped body according to claim 17 , wherein the shape of the shaped body is an automobile outer plate member, a bottle or a container. The molded body according to claim 13 or 14 , wherein the molded body is a molded body manufactured by an extrusion molding method. The shaped body according to claim 19 , wherein the shaped body is a tube or a pipe.   The polyphenylene oxide-based resin composition molded body according to claim 13 or 14, wherein the molded body has a shape of a film.